RU2706684C1 - Hydrogenating catalyst, as well as production thereof and use thereof - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to a catalyst for producing ethylene glycol via oxalate hydrogenation, wherein the catalyst contains (a) an active component in form of nanoparticles which contain copper, wherein the active component is present in concentration of 5 to 35 wt%; (b) an auxiliary substance in form of nanoparticles which contain an element selected from a group consisting of nickel, cobalt, manganese, zinc, aluminum, zirconium, cerium, lanthanum, molybdenum, vanadium, bismuth, boron and phosphorus, wherein the auxiliary substance is present in concentration from 0.01 to 20 wt%; and (c) a carrier in form of hollow microspheres of mesoporous silicon dioxide, on surfaces of which active compound nanoparticles and auxiliary substance nanoparticles are dispersed, wherein said microspheres have average particle diameter of 50 to 5,000 nm and average thickness of outer shell of 5 to 500 nm, wherein said catalyst has specific surface area of 100 to 1,200 m²/g. Invention also relates to a method of producing the disclosed catalyst and a method of producing ethylene glycol.

EFFECT: high conversion ratio of oxalate and high selectivity with respect to ethylene glycol.

11 cl, 2 tbl, 1 ex

Description

FIELD OF THE INVENTION

This invention relates to a catalyst used in the field of organic synthesis, in particular to a catalyst for the gas-phase hydrogenation of oxalate to ethylene glycol, as well as to a method for its preparation and its applications.

BACKGROUND OF THE INVENTION

Ethylene glycol is an important basic organic chemical material capable of reacting with terephthalic acid (OTC), resulting in the formation of polyethylene terephthalate (PET), also known as polyester resin, which is the raw material for polyester fiber and polyester plastic. This is the main area of application of ethylene glycol. Ethylene glycol can also be used directly as an antifreeze or as a coolant for engine preparation. Ethylene glycol dinitrate can be used as an explosive, as well as an integral component of plasticizers, paints, binders, surfactants, explosives and capacitor electrolytes. The current industrial technological route for producing ethylene glycol is to produce ethylene oxide from petroleum ethylene by gas-phase oxidation via the petroleum technological route followed by hydrogenation, which results in an ethylene glycol product. However, given the resource base of China, characterized by "low-quality oil, small volumes of gas and rich sources coal ”, the large-scale production of ethylene glycol products through the oil technological route is reflected in the production of ethylene and other chemical products, and, accordingly, the practical importance and strategic potential in China has the development of methods for producing ethylene glycol from synthesis gas.

Among the reports on various methods for the synthesis of ethylene glycol, a technological route has gradually matured, including the synthesis of oxalic acid diester using CO, followed by hydrogenation of the oxalic acid diester to ethylene glycol. At the end of 2009, an industrial demonstration plant with a capacity of 200,000 tons was completed in the high-tech development zone in the city of Tongliao in the Inner Mongolia Autonomous Region, which successfully produced high-quality ethylene glycol products, thereby announcing that the coal-based technology for producing ethylene glycol officially moved to the level large industrial scale.

One of the key technologies for producing ethylene glycol from coal-based synthesis gas is the development of a catalyst for the hydrogenation of oxalate to ethylene glycol. The Fujian Institute of Physical Sciences, the PRC Academy of Sciences, East China University of Science and Technology, Zhejiang University, Tianjin University and other relevant research institutes have been conducting research on oxalate hydrogenation catalysts since the 1980s. Using a Cu-Cr catalyst at a temperature of from 208 to 230 ° C and a pressure of from 2.5 to 3.0 MPa, a type test was carried out for the hydrogenation of diethyl oxalate. The reaction result showed a diethyl oxalate conversion of 99.8%. With an average selectivity of 95.3%, the duty cycle of the claimed catalyst can be 1,134 hours. The patent issued in the territory of the People's Republic of China under No. 101342489 A, describes a hydrogenation catalyst based on copper and silicon, which contains an auxiliary substance, which can be one or more of alkaline earth metals, chemical elements that are transition metals, or chemical elements being rare-earth metals, moreover, such a catalyst provides a conversion factor of raw materials of more than 99% and selectivity for ethylene glycol of more than 95% at a reaction pressure of 3.0 M but also in terms of liquid complex polybasic acid ester with a space-time velocity of 0.7 h ^-1. The patent, issued in the territory of the People's Republic of China under No. 101138725 B, describes a catalyst for the hydrogenation of an oxalate ester for the synthesis of ethylene glycol, as well as a method for producing such a catalyst, comprising a copper element as an active component and a zinc element as an auxiliary substance, whereby such a catalyst is prepared by the method impregnation, and the catalyst itself provides an oxalate conversion coefficient of about 95% and an ethylene glycol selectivity of about 90%. The patent, issued in the territory of the People's Republic of China under No. 102350348 B, describes a copper-based catalyst which is intended to produce ethylene glycol by hydrogenation of oxalate, as well as a method for producing such a catalyst. In this catalyst, a copper element is used as the active component, and a mesoporous silicon shell, which is formed by in situ compounding, is used as a carrier. Its conversion rate for oxalic acid ester is at least 99%, and the selectivity for ethylene glycol is at least 94%.

In existing catalysts for the hydrogenation of oxalate to ethylene glycol, copper is the most active component, and the content of active metallic copper is generally relatively high. Excessive copper content in them, as a rule, leads to the growth of surface crystals of copper and their activity, and, consequently, to a decrease in the activity and service life of the catalyst and the impossibility of long-term operation of industrial plants.

Therefore, there remains a need for catalysts having activity and stability in the production of ethylene glycol.

SUMMARY OF THE INVENTION

The present invention provides a hydrogenation catalyst for producing ethylene glycol by hydrogenation of an oxalate, as well as a method for producing and using such a catalyst.

It proposes a catalyst for producing ethylene glycol by hydrogenation of oxalate. This catalyst contains an active component in the form of nanoparticles containing copper or copper oxide; excipient in the form of nanoparticles containing an element selected from the group consisting of nickel, cobalt, manganese, zinc, aluminum, zirconium, cerium, lanthanum, molybdenum, barium, vanadium, titanium, iron, yttrium, niobium, tungsten, tin, bismuth , strontium, boron and phosphorus; and a carrier in the form of hollow microspheres of silicon dioxide, on the surfaces of which nanoparticles of the active component and nanoparticles of the excipient are dispersed.

The catalyst may have a specific surface area of from 100 to 900 m ² / g. The catalyst may include an active component, the content of which is from 5 to 35 weight. % The catalyst may include an auxiliary substance, the content of which is from 0.01 to 20 weight. % The oxalate may be dimethyl oxalate, diethyl oxalate, or a combination thereof.

A method of obtaining a catalyst for the production of ethylene glycol by hydrogenation of oxalate. This method includes: (a) adding a copper solution to the element / dispersant precursor solution to obtain a solution III; (b) adding to the precursor solution of the carrier cetyltrimethylammonium bromide (CTAB), a template substance, and then ammonia water to obtain a mixture of IV; (c) adding solution III to mixture IV in the presence of gaseous nitrogen and under heating conditions to obtain a reaction product; (d) dehydration of the reaction product to obtain precipitated phases; (e) washing and drying the precipitated phases to obtain a cured product; and (f) calcining the cured product to thereby obtain a catalyst having a hollow silica microsphere structure.

The specified element / dispersant precursor solution may have a pH of from 1.0 to 7.0. The method may further include adding an element precursor to the deionized water to obtain an element precursor solution, and adding a dispersant element to the precursor solution to obtain an element / dispersant precursor solution. The chemical element may be an element selected from the group consisting of nickel, cobalt, manganese, zinc, aluminum, zirconium, cerium, lanthanum, molybdenum, barium, vanadium, titanium, iron, yttrium, niobium, tungsten, tin, bismuth, strontium , boron and phosphorus. The dispersant may be selected from the group consisting of citric acid, ammonium citrate, acetic acid, ammonium acetate, malonic acid, succinic acid, tartaric acid, glucose and oxalic acid.

The specified method may further include dissolving in deionized water a soluble copper salt, resulting in the formation of a copper solution. The soluble copper salt may be selected from the group consisting of copper nitrate, copper acetate, copper chloride and copper oxalate.

This method may further include dissolving the carrier precursor in a mixture of anhydrous ethanol and deionized water to form a carrier precursor solution. The carrier precursor may be selected from the group consisting of silica sol, methyl orthosilicate, tetraethyl orthosilicate, propyl orthosilicate and butyl orthosilicate.

The template substance may be a solid template substance supported by a covalent bond. The solid template can be selected from the group consisting of polystyrene, phenol-aldehyde resin, porous silicon, activated carbon, polymethyl methacrylate and bisphenol A epoxy.

Moreover, a method for producing ethylene glycol is provided. This method involves the hydrogenation of oxalate to ethylene glycol in the presence of hydrogen and the catalyst of the present invention. Oxalate can be converted with an average degree of conversion of at least 99.0% for at least 2000 hours. The catalyst may have an average selectivity of ethylene glycol of at least 95.0% for at least 2000 hours. Ethylene glycol can be obtained with an average yield of at least 600.0 mg / g cat./h for at least 2000 hours. The oxalate may be dimethyl oxalate. The catalyst may have an average particle size of from 250 to 850 microns.

DETAILED DESCRIPTION OF THE INVENTION

The present invention provides a catalyst for the hydrogenation of oxalate to ethylene glycol, as well as a method for its preparation and its use. The specified catalyst contains an active component, an auxiliary substance and a carrier. The inventors unexpectedly found that to obtain a catalyst having a structure based on hollow microspheres of silicon dioxide, so that such a catalyst has a large specific surface area, you can use a solid template substance. Metal particles of the active component are dispersed on the surface of silicon dioxide microspheres, thereby reducing the load on the metal side. The inventors unexpectedly found that to facilitate the migration of active nanoparticles between the active component, excipient and carrier, so that between the active metal, excipient and the carrier, the adhesion strength is improved, so that the likelihood of sintering and aggregation of the active metal is reduced, and also the stability of the catalyst, dispersant may be used. The hydrogenation catalyst of the invention can be used to hydrogenate oxalate to ethylene glycol, which catalyst provides a high conversion rate of oxalate, high selectivity for ethylene glycol, and strong stability, and is therefore suitable for industrial use.

It proposes a catalyst for producing ethylene glycol by hydrogenation of an oxalate. The specified catalyst contains an active component, an auxiliary substance and a carrier. The oxalate may be dimethyl oxalate, diethyl oxalate, or a combination thereof. In one embodiment, the implementation of the catalyst consists of an active component, excipient and carrier. The catalyst may have a specific surface area of from about 100 to 1200 m ² / g, preferably from about 170 to 1070 m ² / g, and more preferably from about 210 to 980 m ² / g.

As used herein, the term “active component” refers to a substance present in a catalyst that catalyzes the hydrogenation of oxalate to ethylene glycol. The active component may be from about 5 to 35 weight. %, preferably from about 7.5 to 34 weight. %, and more preferably from about 11 to 34% weight. % catalyst. The active component may be in the form of nanoparticles. To obtain the active component present in the catalyst, a soluble copper salt can be used. Such a soluble copper salt may be copper nitrate, copper acetate, copper chloride or copper oxalate, preferably copper nitrate, copper acetate or copper chloride, and more preferably copper nitrate or copper chloride. A copper solution (solution II) can be obtained by dissolving a soluble copper salt in deionized water. Solution II may contain a copper salt in a concentration of from about 0.001 to 2,000 g / ml, based on the total weight of the solution.

As used herein, the term “excipient” refers to a substance present in a catalyst that facilitates the interaction between the active component present in such a catalyst and a carrier. Mentioned excipient may be a chemical element selected from the group consisting of nickel, cobalt, manganese, zinc, aluminum, zirconium, cerium, lanthanum, molybdenum, barium, vanadium, titanium, iron, yttrium, niobium, tungsten, tin, bismuth, strontium, boron and phosphorus. The excipient may be from about 0.01 to about 20 weight. %, preferably from about 0.15 to 18 weight. %, and more preferably from about 0.35 to 14% weight. % catalyst. The active component may be in the form of nanoparticles.

As used herein, the term “element precursor” refers to a substance represented as a specific element that is intended to provide a catalyst with an auxiliary substance. The element may be an element selected from the group consisting of nickel, cobalt, manganese, zinc, aluminum, zirconium, cerium, lanthanum, molybdenum, barium, vanadium, titanium, iron, yttrium, niobium, tungsten, tin, bismuth, strontium, boron and phosphorus. The element precursor may be an oxo acid, chloride, nitrate salt, acetate salt, oxalate salt or ammonium salt, preferably chloride, nitrate salt, acetate salt or ammonium salt, and more preferably chloride, nitrate salt or ammonium salt. A mixture of the element precursor can be obtained by adding the element precursor to deionized water. The precursor element mixture may contain the precursor element in a concentration ranging from about 0.0001 to 1,000 g / ml based on the total weight of the solution.

As used herein, the term “carrier” refers to a substance present in a catalyst that provides a basis for the active component and excipient. The carrier comprises one or more hollow silica microspheres. Silicon hollow microspheres are formed by the formation of covalent bonds by silicon dioxide. The microspheres themselves can have an average particle diameter of from about 50 to 5000 nm, preferably from about 100 to 2500 nm, and more preferably from about 150 to 1050 nm. The microspheres can be composed of a shell that envelops a hollow structure. The microspheres can have an average outer shell thickness of about 5 to 500 nm, preferably about 10 to 350 nm, and more preferably about 20 to 210 nm.

Nanoparticles of the active component and nanoparticles of the excipient are dispersed on the surface of such microspheres. On the surface of such microspheres, for example, nanoparticles of the active component and nanoparticles of the excipient are dispersed.

As used herein, the term “carrier precursor” refers to a substance present in a carrier precursor solution that is used to provide the catalyst with a carrier. The carrier precursor is at least one of substances such as silicon dioxide, methyl orthosilicate, tetraethyl orthosilicate, propyl orthosilicate or butyl orthosilicate, preferably substances such as silicon dioxide, methyl orthosilicate or tetraethyl orthosilicate, and more preferably substances such as silicon dioxide or tetraethyl orthosilicate. A carrier precursor solution can be prepared by dissolving the carrier precursor in a mixture of anhydrous ethanol and deionized water. The carrier precursor solution may contain a carrier precursor in a concentration ranging from about 0.001 to 1,000 g / ml based on the total weight of the solution. The carrier precursor solution may have a pH in the range of about 1.0 to about 7.0.

As used herein, the term “dispersant” refers to a substance that promotes the migration of active nanoparticles between the active component, excipient and carrier. The dispersant may be selected from the group consisting of citric acid, ammonium citrate, acetic acid, ammonium acetate, malonic acid, succinic acid, tartaric acid, glucose or oxalic acid, preferably citric acid and ammonium citrate, preferably selected from the group in which includes ammonium acetate, malonic acid, tartaric acid and glucose, and more preferably selected from the group consisting of at least one of such substances as citric acid, ammonium acetate, tartaric acid and glucose. The element precursor / dispersant solution (solution I) can be obtained by adding the dispersant to the element precursor mixture. Solution I having a pH in the range of about 1.0 to 7.0. Solution I may contain an element precursor in a concentration ranging from about 0.0001 to 1.0000 g / ml and / or a dispersant in a concentration ranging from about 0.0001 to 1.0000 g / ml.

As used herein, the term “template substance” refers to a substance that, in the synthesis of a catalyst, acts as a kind of copier to form a structure. A template may be a solid template substance supported by a covalent bond. The solid template may be polystyrene, phenolic resin, porous silicon, activated carbon, polymethyl methacrylate and bisphenol A epoxy, preferably polystyrene, phenolic resin, activated carbon or polymethyl methacrylate, and more preferably polystyrene, phenolic resin or activated carbon.

For each catalyst in the framework of the present invention offers its own method of production. The claimed method includes: (a) adding a copper solution (solution II) to the element / dispersant precursor solution (solution I), as a result of which solution III is formed; (b) adding cetyltrimethylammonium bromide (CTAB) carrier material, a template substance and ammonia water to the precursor solution, resulting in a mixture of IV; (c) adding solution III to mixture IV in the presence of gaseous nitrogen and under heating conditions, resulting in the formation of a reaction product; (d) dehydration of the reaction product, resulting in the formation of precipitated phases; (e) washing and drying the precipitated phases, resulting in a cured product; and (f) calcining the cured product. The result is a catalyst having a structure based on hollow silicon dioxide microspheres.

In step (1), the copper solution (solution II) is added dropwise, at a constant speed and with continuous vigorous stirring, to the element / dispersant precursor solution (solution I), as a result of which solution III is formed.

In step (2), cetyltrimethylammonium bromide (CTAB) and a template substance can be added to the carrier precursor solution with stirring and at a temperature of about 30 to 50 ° C over about 20 to 60 minutes, and then with intensive stirring at a temperature from about 30 to 60 ° C. over about 1 to 6 hours, ammonia water may be added, resulting in a mixture of IV. In mixture IV, the mass ratio of the carrier precursor: absolute ethanol: deionized water: cetyltrimethylammonium bromide (CTAB): template substance: ammonia water can be about 1: (0.1-50) :( 0.1-50) :( 0.01 -1.0) :( 0.01-5.0) :( 0.01-20.0).

In step (3), nitrogen gas can be introduced into the mixture of solution III and mixture IV for about 5 to 60 minutes with continuous vigorous stirring of such a mixture with further heating for about 1 to 24 hours to a temperature of about 40 to 70 ° C, resulting in the formation of a reaction product.

In step (4), the reaction product can be dehydrated by centrifugation, resulting in the formation of precipitated phases.

In step (5), the precipitated phases can be thoroughly washed with deionized water and dried for about 2 to 24 hours at a temperature of about 50 to 110 ° C and under a pressure of about 80 to 90 kPa, resulting in a cured product .

In step (6), the cured product can be calcined in air for about 2 to 8 hours at a temperature of about 350 to 700 ° C.

Moreover, a method for producing ethylene glycol is provided. This method involves the hydrogenation of oxalate in the presence of hydrogen and the catalyst of the present invention. The oxalate may be dimethyl oxalate, diethyl oxalate, or a compound thereof. For example, the inventive catalyst can be used to hydrogenate dimethyl oxalate to ethylene glycol. The catalyst may be compressed, extruded, sprayed and centrifuged to form particles of about 1 to 6 mm in size, for example, cylindrical, spherical, ellipsoidal, toroidal, honeycomb, gear, clover-like and four-petal, with further grinding and screening of particles of about 20 up to 60 mesh The catalyst may have an average particle size of from about 250 to about 850 microns.

The cured catalyst is compressed. This reaction can be carried out in a fixed bed reactor installation under reducing conditions. Reduction conditions include a gas mixture of nitrogen with hydrogen, the hydrogen content of which is about 5% of the total volume of the gas mixture, the temperature is from about 180 to 300 ° C, and the spatio-temporal velocity of the gas is from about 500 to 1,500 hours ^{- 1} for about 6 to 30 hours. The conditions of reduction include a temperature of about 170 to 210 ° C, a pressure of about 1 to 3.5 MPa, as well as a molar ratio of hydrogen to ether of about 30 to 120, a methanol solution with a dimethyl oxalate content of about 5 to 100% of the total weight of the methanol solution at a temporal-spatial velocity of the liquid from 0.5 to 3.0 hour ^-1 .

The hydrogenation catalyst of the present invention has a structure based on hollow silica microspheres and provides a high conversion rate of oxalate, high selectivity for ethylene glycol, strong stability and high yield of ethylene glycol.

As used herein, the term “conversion rate” refers to the percentage of oxalate converted to product. The average conversion rate exhibited by the catalyst in accordance with the present invention may be at least about 98.0%, 98.5%, 99.0%, 99.5%, 99.9% or 100% over a period of time, for example, with a duration of at least 500, 1000, 1500, 2000, 2500, 3000, 3500, 4000, 4500, 5000, 5500, 6000, 7000, 8000, 9000 or 10,000 hours. The average conversion rate of oxalate can be at least about 1%, 2%, 3%, 4%, or 5% or more over a period of time, for example, a duration of at least about 500, 1000, 1500, 2000, 2500, 3000, 3500, 4000, 4500, 5000, 5500, 6000, 7000, 8000, 9000 or 10,000 hours when using the catalyst of the present invention, compared with a catalyst having a specific surface area of less than about 1, 10 or 100 m ² / g, or a catalyst obtained by a method not involving the use of a dispersant, a template substance, or their readings.

As used herein, the term “selectivity” refers to the percentage of oxalate converted to the target product of the total volume of converted oxalate. The average catalyst selectivity for ethylene glycol in accordance with the present invention may be at least about 95.0%, 96.0%, 97.0%, 98.0%, 99.0%, 99.5%, 99, 9% or 100% over a period of time, for example, a duration of at least about 500, 1000, 1500, 2000, 2500, 3000, 3500, 4000, 4500, 5000, 5500, 6000, 7000, 8000, 9000 or 10,000 hours. The average coefficient of selectivity of the catalyst for ethylene glycol can be at least about 1%, 2%, 3%, 4%, or 5% and higher over a period of time, for example, a duration of at least about 500, 1000, 1500, 2000, 2500 , 3000, 3500, 4000, 4500, 5000, 5500, 6000, 7000, 8000, 9000 or 10,000 hours when using the catalyst of the present invention, compared with a catalyst having a specific surface area of less than about 1, 10 or 100 m ² / g, or a catalyst obtained by the method, not involving the use of dispersion one templating agent, or combinations thereof.

As used herein, the term “temporal-spatial yield of ethylene glycol” refers to the amount of ethylene glycol produced per unit mass of catalyst per unit time. The average yield of ethylene glycol in accordance with the present invention can be at least about 500, 600, 700, 800, 900 or 1000 mg / g cat. / Hour over a period of time, for example, a duration of at least about 500, 1000, 1500, 2000 , 2500, 3000, 3500, 4000, 4500, 5000, 5500, 6000, 7000, 8000, 9000 or 10,000 hours. The average yield of ethylene glycol can be at least about 50, 100, 200, 300, 400, 500, 600, 700, 800, 900 or 1000 mg / g cat. / Hour and above over a period of time, for example, at least about 500, 1000, 1500, 2000, 2500, 3000, 3500, 4000, 4500, 5000, 5500, 6000, 7000, 8000, 9000 or 10,000 hours when using the catalyst of the present invention, compared with a catalyst having a specific area surface less than about 1, 10 or 100 m ² / g, a catalyst obtained by a method not comprising the use of a dispersant, templatnog substances or combinations thereof.

The term “about”, as used herein when referring to a measured value, for example, quantity, percent, and the like, is intended to encompass deviations within ± 20% or ± 10%, more preferably ± 5%, even more preferably ± 1 % and even more preferably ± 0.1% of the indicated value, since such deviations correspond to the norm.

Example 1

Catalysts 1-11 were prepared, as well as comparative samples of catalysts 1-4. Using the ICP MS method, the content of the active component for each catalyst was measured (Tables 1 and 2). Using a physicochemical adsorption meter, the specific surface area of each catalyst was measured (table 1). Scanning electron microscopy was used to measure the particle size and wall thickness of the shell of the hollow microspheres of silicon dioxide (table 1). For each catalyst, catalytic activity was determined (e.g., dimethyl oxalate conversion coefficient and ethylene glycol selectivity) in the hydrogenation reaction of dimethyl oxalate, resulting in ethylene glycol (table 2). In the hydrogenation reaction for catalysts 1-10 and comparative samples of catalysts 1-3, a methanol-containing dimethyl oxalate solution was used as a starting material, and dimethyl oxalate was used as a starting material for catalyst 11 and a comparative sample of catalyst 4.

Catalyst 1

Catalyst 2 was obtained in accordance with the production method, comprising the following steps:

(1) dissolving 2.55 g of cobalt nitrate in 100 ml of deionized water, adding 14.22 g of citric acid, followed by adjusting the pH to a value of 3.5, resulting in a solution of I;

(2) dissolving in 200 ml of deionized water 9.81 g of copper nitrate, resulting in a solution of II; and then adding solution II to solution I at a constant rate and with vigorous stirring, resulting in a solution of III;

(3) dissolving 19.40 g of ethylorthosilicate 32 in 150 ml of absolute ethanol and 50 ml of deionized water, adding 6.44 g of cetyltrimethylammonium bromide (CTAB), and also, as a template, 7.82 g of polystyrene microspheres with stirring for 40 min at a temperature of 40 ° C, and then adding with vigorous stirring at a temperature of 50 ° C for 4 hours 73.54 g of ammonia, resulting in a mixture of IV;

(4) adding solution III to mixture IV, introducing nitrogen gas for 30 minutes with continuous vigorous stirring, heating for 12 hours to a temperature of 65 ° C, dehydration of the reaction product by centrifugation, and thorough washing with deionized water at a temperature of 80 ° C and under a pressure of 85 kPa; drying for 8 hours, resulting in a cured product, sintering the cured product in air at 500 ° C for 4 hours, resulting in a catalyst 1 having a structure of hollow silicon dioxide microspheres.

The catalytic activity of catalyst 1 was determined in the following hydrogenation reaction: catalyst 1 was pelletized and ground, followed by sieving particles from 20 to 60 mesh in size, and then was placed in a fixed-bed reactor for 24 hours under reducing conditions of a gas mixture of nitrogen and hydrogen containing 5 % hydrogen at a temperature of 220 ° C and with a space-time velocity of 700 hours ^-1 ; the reaction temperature was 185 ° C; reaction pressure - 2.0 MPa; the molar ratio of hydrogen to ester is -80; and the temporal-spatial velocity of the liquid solution of methanol containing dimethyl oxalate at the level of 80% of the total weight of the methanol solution itself was 1.5 h ^-1 .

Comparative Catalyst 1

A comparative sample of catalyst 1 was obtained in accordance with the method of producing catalyst 1, except that the citric acid acting as a dispersant was not added in step (1). The conditions for evaluating the catalytic activity were identical to those of catalyst 1.

Catalyst 2

Catalyst 2 was obtained in accordance with the method of preparation of catalyst 1, except that in step (3) the polystyrene microspheres were replaced with activated carbon and the cobalt nitrate was replaced with nickel nitrate.

The catalytic activity of catalyst 2 was determined in the following hydrogenation reaction: catalyst 2 was pelletized and ground, followed by sieving particles from 20 to 60 mesh in size, and then was placed in a fixed-bed reactor for 24 hours under reducing conditions of a nitrogen and hydrogen gas mixture containing 5 % hydrogen at a temperature of 240 ° C and with a space-time velocity of 1000 h ^-1 ; the reaction temperature was 200 ° C; reaction pressure - 1.5 MPa; the molar ratio of hydrogen to ester is 100; and the temporal-spatial velocity of the methanol solution in the liquid state containing dimethyl oxalate at the level of 50% of the total weight of the methanol solution itself was 2.0 h ⁻¹ .

Comparative Catalyst 2

A comparative sample of catalyst 2 was obtained in accordance with the method for producing catalyst 2, except that activated carbon was not added in step (3). The conditions for evaluating the catalytic activity were identical to the similar conditions for sample 2.

Catalyst 3

Catalyst 3 was prepared according to the preparation of catalyst 1, except that in step (3) the polystyrene microspheres were replaced with a phenol-aldehyde resin and the cobalt nitrate was replaced with cerium nitrate.

The catalytic activity of catalyst 3 was determined in the following hydrogenation reaction: catalyst 3 was pelletized and ground, followed by sieving particles from 20 to 60 mesh in size, and then was placed in a fixed-bed reactor for 20 hours under reducing conditions of a nitrogen and hydrogen gas mixture containing 5 % hydrogen at a temperature of 200 ° C and with a space-time velocity of 1200 hours ^-1 ; the reaction temperature was 195 ° C; reaction pressure - 2.5 MPa; the molar ratio of hydrogen to ester is 120; and the temporal-spatial velocity of the liquid solution of methanol containing dimethyl oxalate at the level of 75% of the total weight of the methanol solution itself was 1.0 hour ^-1 .

Comparative Catalyst 3

A comparative sample of catalyst 3 was obtained in accordance with the method for producing catalyst 3, except that the citric acid in step (1) and the phenol-aldehyde resin in step (3) were not used as a dispersant. The conditions for evaluating the catalytic activity were identical to those of sample 3.

Catalyst 4

Catalyst 4 was prepared according to the preparation of catalyst 1, except that in step (3) the polystyrene microspheres were replaced with porous silicon and the cobalt nitrate was replaced with lanthanum nitrate.

The catalytic activity of catalyst 4 was determined in the following hydrogenation reaction: catalyst 4 was pelletized and ground, followed by sieving particles from 20 to 60 mesh in size, and then was placed in a fixed-bed reactor for 22 hours under reducing conditions of a nitrogen and hydrogen gas mixture containing 5 % hydrogen at a temperature of 210 ° C and with a space-time velocity of 800 hours ^-1 ; the reaction temperature was 205 ° C; reaction pressure - 2.0 MPa; the molar ratio of hydrogen to ester is 60; and the temporal-spatial velocity of the methanol solution in the liquid state containing dimethyl oxalate at the level of 95% of the total weight of the methanol solution itself was 1.2 h ⁻¹ .

Catalyst 5

Catalyst 5 was prepared according to the preparation of catalyst 1, except that in step (3) the polystyrene microspheres were replaced with polymethyl methacrylate and the cobalt nitrate was replaced with the molybdenum ammonium salt.

The catalytic activity of catalyst 5 was determined in the following hydrogenation reaction: catalyst 5 was pelletized and crushed, followed by sieving particles from 20 to 60 mesh in size, and then was placed in a fixed-bed reactor for 10 hours under reducing conditions of a nitrogen and hydrogen gas mixture containing 5 % hydrogen at a temperature of 220 ° C and with a space-time velocity of 1000 h ^-1 ; the reaction temperature was 175 ° C; reaction pressure - 3.5 MPa; the molar ratio of hydrogen to ester is 120; and the temporal-spatial velocity of the methanol solution in the liquid state containing dimethyl oxalate at the level of 100% of the total weight of the methanol solution itself was 0.8 h ⁻¹ .

Catalyst 6

Catalyst 6 was obtained in accordance with the method of preparing catalyst 1, except that in step (3) the polystyrene microspheres were replaced with bisphenol A epoxy and the cobalt nitrate was replaced with manganese nitrate.

The catalytic activity of catalyst 6 was determined in the following hydrogenation reaction: catalyst 6 was pelletized and crushed, followed by sieving particles from 20 to 60 mesh in size, and then for 20 hours it was placed in a fixed-bed reactor under reducing conditions of a nitrogen and hydrogen gas mixture containing 5 % hydrogen at a temperature of 190 ° C and with a space-time velocity of 1,500 h ^-1 ; the reaction temperature was 190 ° C; reaction pressure - 2.5 MPa; the molar ratio of hydrogen to ester is 100; and the temporal-spatial velocity of the methanol solution in the liquid state containing dimethyl oxalate at the level of 25% of the total weight of the methanol solution itself was 2.0 h ⁻¹ .

Catalyst 7

Catalyst 7 was prepared according to the preparation of catalyst 1, except that in step (1) citric acid was replaced with glucose and cobalt nitrate was replaced with zirconium nitrate.

The catalytic activity of catalyst 7 was determined in the following hydrogenation reaction: catalyst 7 was pelletized and ground, followed by sieving particles from 20 to 60 mesh in size, and then was placed in a fixed-bed reactor for 24 hours under reducing conditions of a nitrogen and hydrogen gas mixture containing 5 % hydrogen at a temperature of 230 ° C and with a space-time velocity of 1200 hours ^-1 ; the reaction temperature was 195 ° C; reaction pressure - 2.0 MPa; the molar ratio of hydrogen to ester is 110; and the temporal-spatial velocity of the liquid solution of methanol containing dimethyl oxalate at the level of 60% of the total weight of the methanol solution itself was 1.8 h ⁻¹ .

Catalyst 8

Catalyst 8 was prepared according to the preparation of catalyst 1, except that the citric acid added in step (1) was replaced with tartaric acid and the cobalt nitrate was replaced with zinc nitrate.

The catalytic activity of catalyst 8 was determined in the following hydrogenation reaction: catalyst 8 was pelletized and ground, followed by sieving particles from 20 to 60 mesh in size, and then placed in a fixed-bed reactor under reducing conditions that provided a temperature of 240 ° C and a spatio-temporal space a speed of 1000 h ⁻¹ , a mixture of nitrogen and hydrogen containing 5% hydrogen, wherein such a gas mixture was reduced for 22 hours; the reaction temperature was 180 ° C, the reaction pressure was 3.0 MPa, the molar ratio of hydrogen to ester was 120, and the temporal-spatial velocity of the methanol solution in the liquid state with a dimethyl oxalate mass concentration of 90% was 1.1 hours ^-1 .

Catalyst 9

Catalyst 9 was prepared according to the preparation of catalyst 1, except that the citric acid added in step (1) was replaced with ammonium acetate and the cobalt nitrate was replaced with aluminum nitrate and boric acid.

The catalytic activity of catalyst 9 was determined in the following hydrogenation reaction: catalyst 9 was pelletized and ground, followed by sieving particles from 20 to 60 mesh in size, and then placed in a fixed-bed reactor under reducing conditions that provided a temperature of 200 ° C and a spatio-temporal space a speed of 1,100 h ⁻¹ , a mixture of nitrogen and hydrogen containing 5% hydrogen, the gas mixture being reduced for 16 hours; the reaction temperature was 210 ° C, the reaction pressure was 1.5 MPa, the molar ratio of hydrogen to ester was 90, and the temporal-spatial velocity of the methanol solution in the liquid state with a dimethyl oxalate mass concentration of 55% was 0.7 hour ^-1 .

Catalyst 10

Catalyst 10 was prepared according to the preparation of catalyst 1, except that the citric acid added in step (1) was replaced with malonic acid and the cobalt nitrate was replaced with barium nitrate and ammonium hydrogen phosphate.

The catalytic activity of catalyst 10 was determined in the following hydrogenation reaction: catalyst 10 was pelletized and ground, followed by sieving particles from 20 to 60 mesh in size, and then placed in a fixed-bed reactor under reducing conditions that provided a temperature of 280 ° C and a spatio-temporal space a speed of 900 h ⁻¹ , a mixture of nitrogen and hydrogen containing 5% hydrogen, the gas mixture being reduced for 30 hours; the reaction temperature was 170 ° C, the reaction pressure was 1.0 MPa, the molar ratio of hydrogen to ester was 30, and the temporal-spatial velocity of the methanol solution in the liquid state with a dimethyl oxalate mass concentration of 55% was 0.7 hour ^-1 .

Catalyst 11

Catalyst 10 was prepared according to the preparation of catalyst 1, except that cobalt nitrate was replaced with bismuth nitrate and lanthanum nitrate.

The catalytic activity of catalyst 11 was determined in the following hydrogenation reaction: catalyst 11 was pelletized and crushed, followed by sieving particles from 20 to 60 mesh in size, and then placed in a fixed-bed reactor under reducing conditions that provided a temperature of 230 ° C and a spatio-temporal space a speed of 800 h ⁻¹ , a mixture of nitrogen and hydrogen containing 5% hydrogen, the gas mixture being reduced for 24 hours; the reaction temperature was from 185 to 195 ° C, the reaction pressure was 2.5 MPa, the molar ratio of hydrogen to ester was from 80 to 100, and the temporal-spatial velocity of the dimethyl oxalate in the liquid state was from 1.0 to 2, 0 hour ^-1 .

A liquid sample was taken every hour to analyze the composition of the product by gas chromatography, and the conversion coefficient of dimethyl oxalate and selectivity for ethylene glycol were calculated. The reaction was stable for 6000 hours, and the activity of the catalyst was significantly reduced. The average conversion coefficient of dimethyl oxalate reached 99.9%, the average selectivity for ethylene glycol was more than 96.5%, and the average yield of ethylene glycol was not less than 759.8 mg / g cat / hour. The catalyst showed excellent hydrogenation activity, ethylene glycol selectivity and stability, and therefore is suitable for industrial use.

Comparative Catalyst 4

A comparative sample of catalyst 4 was obtained in accordance with the method of preparation of catalyst 11, except that the citric acid acting as a dispersant in step (1) and the polystyrene microspheres in step (3) were not added. The conditions for evaluating the activity of the catalyst were identical to those of catalyst 11. After 2000 hours of reaction, the activity of the catalyst decreased significantly. The conversion coefficient of dimethyl oxalate decreased from 97.8% to 93.9%, and the selectivity for ethylene glycol decreased from 94.6% to 88.7%. The average yield of ethylene glycol was only 583.3 mg / g cat / hour.

Although the claimed invention is illustrated and described herein with reference to specific embodiments, it is not limited to the demonstrated characteristics. Conversely, various changes may be made to these characteristics within the scope and range of equivalents of the claims without departing from the invention itself.

Claims (27)

1. A catalyst for producing ethylene glycol by hydrogenation of an oxalate containing: (a) an active component in the form of nanoparticles that contain copper, wherein the active component is present in a concentration of from 5 to 35 weight. %; (b) an excipient in the form of nanoparticles, which contain an element selected from the group consisting of nickel, cobalt, manganese, zinc, aluminum, zirconium, cerium, lanthanum, molybdenum, vanadium, bismuth, boron and phosphorus, and the excipient is present in concentration from 0.01 to 20 weight. %; and (c) a carrier in the form of hollow microspheres of mesoporous silica, on the surfaces of which nanoparticles of the active component and nanoparticles of the excipient are dispersed, said microspheres having an average particle diameter of 50 to 5000 nm and an average outer shell thickness of 5 to 500 nm, moreover, said catalyst has a specific surface area of from 100 to 1200 m ² / g. 2. The catalyst according to claim 1, wherein the oxalate is dimethyl oxalate, diethyl oxalate, or a combination thereof. 3. A method of producing a catalyst according to claim 1, including: (a) adding a copper solution to the element / dispersant precursor solution to obtain a solution III; (b) adding to the precursor solution of the carrier of cetyltrimethylammonium bromide (CTAB), a template substance and then ammonia water to obtain a mixture of IV; (c) adding solution III to mixture IV in the presence of gaseous nitrogen and under heating conditions to obtain a reaction product; (d) dehydration of the reaction product to obtain precipitated phases; (e) washing and drying the precipitated phases to obtain a cured product; and (f) calcining the cured product to thereby obtain a catalyst having a hollow silica microsphere structure; wherein said copper solution is a solution of copper nitrate in deionized water, wherein said element precursor is selected from the group consisting of nickel, cobalt, manganese, zinc, aluminum, zirconium, cerium, lanthanum, vanadium or bismuth nitrate, a molybdenum ammonium salt, boric acid and ammonium hydrogen phosphate, wherein said dispersant is selected from the group consisting of citric acid, ammonium acetate, malonic acid, tartaric acid and glucose; moreover, the solution of the precursor element / dispersant has a pH from 1.0 to 7.0; moreover, the solid template substance is selected from the group consisting of polystyrene, phenol-aldehyde resin, porous silicon, activated carbon, polymethyl methacrylate and bisphenol A-based epoxy; and wherein the carrier precursor solution is selected from the group consisting of methyl orthosilicate, tetraethyl orthosilicate, propyl orthosilicate and butyl orthosilicate in a mixture of anhydrous ethanol and deionized water. 4. The method according to claim 3, further comprising adding an element precursor to the deionized water to obtain an element precursor solution, and adding a dispersant element to the precursor solution to obtain an element / dispersant precursor solution. 5. The method of claim 3, further comprising dissolving the soluble copper salt in deionized water to produce a copper solution, wherein the soluble copper salt is copper nitrate. 6. The method of claim 3, further comprising dissolving the carrier precursor in a mixture of anhydrous ethanol and deionized water to form a carrier precursor solution. 7. A method of producing ethylene glycol, including the hydrogenation of oxalate to ethylene glycol in the presence of hydrogen and a catalyst according to claim 1. 8. The method according to p. 7, in which the oxalate is converted with an average degree of conversion of at least 99.0% for at least 2000 hours. 9. The method according to p. 7, in which the catalyst has an average selectivity for ethylene glycol of at least 95.0% for at least 2000 hours. 10. The method according to p. 7, in which ethylene glycol is obtained with an average yield of at least 600.0 mg / g cat./h for at least 2000 hours. 11. The method of claim 7, wherein the oxalate is dimethyl oxalate.